CN113492018B - Resin catalyst for bisphenol A synthesis and application of bisphenol A in catalytic synthesis - Google Patents

Resin catalyst for bisphenol A synthesis and application of bisphenol A in catalytic synthesis Download PDF

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CN113492018B
CN113492018B CN202010251088.XA CN202010251088A CN113492018B CN 113492018 B CN113492018 B CN 113492018B CN 202010251088 A CN202010251088 A CN 202010251088A CN 113492018 B CN113492018 B CN 113492018B
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bisphenol
catalyst
synthesis
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resin catalyst
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CN113492018A (en
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吕晓东
王义成
冷东斌
张伟
彭慧敏
杨松
管秀明
赵吉阳
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Dandong Mingzhu Special Resin Co ltd
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
    • B01J31/08—Ion-exchange resins
    • B01J31/10—Ion-exchange resins sulfonated
    • B01J35/51—
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C37/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
    • C07C37/11—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by reactions increasing the number of carbon atoms
    • C07C37/20—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by reactions increasing the number of carbon atoms using aldehydes or ketones
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
    • B01J2231/40—Substitution reactions at carbon centres, e.g. C-C or C-X, i.e. carbon-hetero atom, cross-coupling, C-H activation or ring-opening reactions
    • B01J2231/42—Catalytic cross-coupling, i.e. connection of previously not connected C-atoms or C- and X-atoms without rearrangement
    • B01J2231/4205—C-C cross-coupling, e.g. metal catalyzed or Friedel-Crafts type
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

Abstract

The patent application provides a resin catalyst for bisphenol A synthesis and application of bisphenol A catalysis preparation. The bisphenol A synthetic resin catalyst is prepared by adding large-aperture sulfonated polystyrene spheres with water content of 45-55% into deionized water, adjusting pH value to 5-7, adding dimercaptoethyl sulfide, modifying reaction for 1-3 hours, and washing with water. In a bisphenol A catalytic reaction device filled with the resin catalyst, the reaction temperature is 80-90 ℃ and the feeding airspeed is 0.2h ‑1 ‑1h ‑1 The pressure is 0.2Mpa-0.4 Mpa. The technical proposal greatly improves the single pass conversion rate of the acetone prepared by synthesizing bisphenol A, reduces the catalyst consumption and reduces the requirement on raw materials.

Description

Resin catalyst for bisphenol A synthesis and application of bisphenol A in catalytic synthesis
Technical Field
The present application relates to polystyrene resins and catalytic modifications and preparation methods thereof and catalytic applications thereof, and in particular to a catalyst for bisphenol a catalytic synthesis, a preparation method thereof and catalytic synthesis applications thereof.
Background
Bisphenol A has very wide application and can be used for producing polycarbonate, epoxy resin and other special resin. Bisphenol A is produced by condensing phenol and acetone serving as reaction raw materials under the condition of an acid catalyst. The production method is divided into a sulfuric acid method, a hydrochloric acid method, a boron fluoride method, a silicon chloride method, a hydrogen chloride method and an ion exchange method according to different catalysts. Although the former direct acid-adding catalytic methods have a good effect despite numerous researches, the industrial practice has the common problem that: the method has the advantages of high energy consumption, high cost, serious equipment corrosion and serious three-waste pollution, and is particularly critical that the product quality is poor, the polycarbonate grade and the food grade can not be achieved, and the method can only be used for producing general epoxy resin and a small amount of flame retardant.
At the end of fifties of the 20 th century, the united states company of carbon company began to study the synthesis of bisphenol a by the ion exchange resin method, and successfully realized commercial application of the cation exchange resin method for bisphenol a synthesis in 1960. The method adopts cationic resin as catalyst to replace acid and alkali catalysts with strong corrosiveness, has the advantages of reduced requirement on equipment materials, reduced side reaction, relatively improved selectivity, simplified product refining process, simple separation of reaction products and the catalyst, less three wastes pollution and high product quality, but has the substantial technical problems of large catalyst consumption, low acetone single pass conversion rate and high requirement on reaction raw materials.
At present, the main production area of bisphenol A is concentrated in Europe and America and Japan, and China is limited by the synthesis technology, so that the bisphenol A and downstream products thereof are imported by throwing away a lot of foreign exchange every year.
Disclosure of Invention
The invention aims to solve the technical problem of low single-pass conversion rate of acetone in the preparation of bisphenol A by a cationic resin catalytic method, and provides a resin catalyst for synthesizing bisphenol A with high and stable catalytic activity, a preparation method thereof and application of bisphenol A in catalytic preparation.
The technical scheme of the resin catalyst for bisphenol A synthesis provided by the patent application comprises the following main technical contents: a resin catalyst for synthesizing bisphenol A is prepared through adding the big-aperture sulfonated polystyrene balls with water content of 45-55% to deionized water, regulating pH value to 5-7, adding dimercaptoethyl sulfide, modifying reaction for 1-3 hr, and water washing.
One preferable technical means of the whole technical scheme is that the pore diameter of the large-pore-diameter sulfonated polystyrene spheres is not less than 10nm.
One preferable technical means of the whole technical scheme is that the weight ratio of the sulfonated polystyrene spheres to deionized water to the dimercaptoethyl sulfide is 100:200:2-10.
One preferable technical means of the whole technical scheme is that the polystyrene white balls before sulfonation of the large-aperture sulfonated polystyrene balls are dried and volatilized to remove the solvent, and the water content in mass percent is 5-10%.
One preferable technical means of the whole technical scheme is that the polystyrene white balls before sulfonation of the large-aperture sulfonated polystyrene balls are sulfonated base balls with the particle size of 0.3-1.2 mm.
One preferable technical means in the whole technical scheme is that the large-aperture sulfonated polystyrene spheres are prepared by mixing polystyrene white spheres with 98% sulfuric acid sulfonating agent according to the mass ratio of 1:8-12, stirring for 0.5-2 h until the mixture is fully mixed, performing sulfonation reaction for 8-20 h at the temperature of 100-120 ℃, cooling after the end, flushing deionized water to be neutral, and separating.
The patent application also provides a preparation method of the resin catalyst for bisphenol A synthesis.
The application also provides bisphenol A catalysis preparation application of the resin catalyst for bisphenol A synthesis, and the application process comprises the following steps: the catalyst is put into a catalytic reaction device, firstly, the water in the catalyst is replaced by a phenol concentrated solution with the concentration not lower than 80%, then, the catalytic synthesis reaction of the acetone and the phenol is carried out, the reaction mole ratio of the phenol and the acetone is 10:1, the reaction temperature is 80-90 ℃, and the feeding airspeed is 0.2h -1 -1h -1 The pressure is 0.2Mpa-0.4 Mpa.
The catalyst comprises a catalyst group, a catalyst-free catalyst group and a catalyst-free catalyst group, wherein the catalyst-free catalyst group comprises a catalyst group, a catalyst-free catalyst group and a catalyst-free catalyst group. The catalyst promoter selected in the application is dimercaptoethyl sulfide with a dimercapto structure, wherein, a sulfydryl and sulfonate of sulfonated polystyrene balls form a firm chemical bond, thereby avoiding loss of sulfydryl and ensuring the stability of the prepared catalyst; the other mercapto group does not react with the sulfonate, and can ionize to produce hydrogen ions, so that the original acidity and high catalyst activity of the sulfonation catalyst are maintained, meanwhile, as the molecular chain of the cocatalyst dimercaptoethyl sulfide is longer, the presented space resistance is larger, the entry of external water can be effectively prevented, while the water is an important factor for preventing the reaction speed, meanwhile, the simple chain structure does not cause the resistance of the resin to be too large, the entry and exit of reactants and products are influenced, the catalysis of bisphenol A synthesis reaction is greatly improved, the single pass conversion rate of acetone prepared by bisphenol A synthesis is obviously improved, the conversion rate of acetone can reach 99.7%, the selectivity can reach 99.1%, and compared with the synthesis application without mercapto modification, the catalyst consumption is reduced, and the requirement on raw materials is also reduced.
Detailed Description
The resin catalyst for bisphenol A synthesis disclosed by the patent application is prepared by modifying large-aperture sulfonated polystyrene spheres by dimercaptoethyl sulfide, and the aperture of the large-aperture sulfonated polystyrene spheres is not less than 10nm.
The present invention will be described in detail and by way of examples, but the scope of protection of the present application is not limited to the following examples.
Example 1:
selecting macroporous polystyrene white balls with the water content of 5% and the particle size of 0.3-1.2 mm as a sulfonation matrix, mixing the white balls with sulfuric acid with the concentration of 98%, stirring the white balls with the mass ratio of 1:8 with a sulfonating agent for 0.5h, fully mixing the white balls with the sulfonating agent, reacting the white balls with the sulfonating agent for 8h at the temperature of 100 ℃, cooling the white balls after the reaction is finished, placing the white balls in a washing column, washing the white balls with deionized water to be neutral, separating sulfonated resin with the water content of 50%, and carrying out sulfhydrylation modification:
adding sulfonated resin into a reaction kettle, adding deionized water, adjusting pH=5, adding a dimercaptoethyl sulfide modifier, carrying out modification reaction for 1 hour, and washing and discharging after the modification reaction is finished to obtain the bisphenol A resin catalyst, wherein the ratio of the sulfonated resin to the deionized water to the dimercaptoethyl sulfide is 100:200:2 in parts by weight.
The obtained resin catalyst is used for bisphenol A catalytic synthesis. Loading 50ml of newly obtained catalyst into a fixed bed reactor, firstly replacing water in the catalyst with a phenol concentrated solution with the concentration not lower than 80%, and then carrying out catalytic synthesis reaction of acetone and phenol, wherein the reaction molar ratio of the phenol to the acetone is 10:1, the reaction temperature is 80 ℃ and the feeding airspeed is 0.2h -1 The reaction was carried out under a pressure of 0.2MPa, and the acetone conversion was 99.8% and the selectivity was 99.3%.
Practical researches prove that the conventional macroporous polystyrene white ball serving as a sulfonated matrix has little influence on the catalyst prepared by bisphenol A catalysis after modification, but the preparation of the macroporous polystyrene white ball is concretely as follows:
1) Polymerization
Weighing styrene, p-ethylstyrene, m-ethylstyrene, p-divinylbenzene, m-divinylbenzene, pore-forming agent and initiator according to the weight parts of table 1, loading into a mixing tank, stirring for 0.5h, and uniformly mixing the feed liquid, wherein the pore-forming agent and the initiator are conventional components, such as white oil is used as the pore-forming agent, and benzoyl peroxide is used as the initiator;
adding a water phase into a polymerization kettle, stirring and heating to 40 ℃ to enable the water phase to be completely dissolved, adding a feed liquid of a mixing tank into the polymerization kettle, stirring at a rotation speed of 50 r/min, slowly heating to 80 ℃ for polymerization reaction for 8 hours, cooling, discharging, and washing the polymerized white balls with hot water and cold water alternately for three times to obtain the polymerized white balls; the water phase is prepared from conventional dispersing agents such as alum;
2) Extracting
Adding the polymeric white balls into an extraction kettle, adding excessive solvent dichloroethane into a distillation kettle, heating to evaporate and condense the solvent in the kettle to the extraction kettle, dissolving the pore-forming agent by the solvent to form a mixed solution, overflowing the liquid level of the mixed solution into the distillation kettle by adopting an overflow method, repeating the steps for 6 times until the pore-forming agent of the polymeric white balls is extracted completely, drying the extracted polymeric white balls until the water content is 5%, and screening out the polymeric white balls with the particle size of 0.3-1.2 mm as sulfonated base balls.
TABLE 1
Example 2:
selecting macroporous polystyrene white balls with the water content of 5% and the particle size of 0.3-1.2 mm as a sulfonation matrix, mixing with sulfuric acid with the concentration of 98%, stirring for 2 hours, fully mixing with a sulfonating agent, reacting for 20 hours at the temperature of 120 ℃, cooling after the reaction is finished, placing in a water washing column, washing with deionized water to be neutral, separating sulfonated resin with the water content of 50%, and carrying out sulfhydrylation modification:
adding sulfonated resin into a reaction kettle, adding deionized water, adjusting pH=5-7, adding a dimercaptoethyl sulfide modifier, carrying out modification reaction for 3 hours, and washing and discharging after the modification reaction is finished to obtain the bisphenol A resin catalyst, wherein the ratio of the sulfonated resin to the deionized water to the dimercaptoethyl sulfide is 100:200:8 in parts by weight.
The obtained resin catalyst is used for bisphenol A catalytic synthesis. Loading 50ml of newly obtained catalyst into a fixed bed reactor, firstly replacing water in the catalyst with a phenol concentrated solution with the concentration not lower than 80%, and then carrying out catalytic synthesis reaction of acetone and phenol, wherein the reaction molar ratio of the phenol to the acetone is 10:1, the reaction temperature is 85 ℃, and the feeding airspeed is 0.8h -1 The reaction was carried out under a pressure of 0.3MPa, and the acetone conversion was 99.7% and the selectivity was 99.1%.
Practical researches prove that the conventional macroporous polystyrene white ball serving as a sulfonated matrix has little influence on the catalyst prepared by bisphenol A catalysis after modification, but the preparation of the macroporous polystyrene white ball is concretely as follows:
1) Polymerization
Weighing styrene, p-ethylstyrene, m-ethylstyrene, p-divinylbenzene, m-divinylbenzene, pore-forming agent and initiator according to the weight parts of table 2, loading into a mixing tank, stirring for 0.5h, and uniformly mixing the feed liquid, wherein the pore-forming agent and the initiator are conventional components, such as white oil is used as the pore-forming agent, and benzoyl peroxide is used as the initiator;
adding a water phase into a polymerization kettle, stirring and heating to 50 ℃ to enable the water phase to be completely dissolved, adding a material liquid of a mixing tank into the polymerization kettle, stirring at a rotation speed of 120 r/min, slowly heating to 80 ℃ for polymerization reaction for 18 hours, cooling, discharging, and washing the polymerized white balls with hot water and cold water alternately for three times to obtain the polymerized white balls; the water phase is prepared from conventional dispersing agents such as alum;
2) Extracting
Adding the polymeric white balls into an extraction kettle, adding excessive solvent dichloroethane into a distillation kettle, heating to evaporate and condense the solvent in the kettle to the extraction kettle, dissolving the pore-forming agent by the solvent to form a mixed solution, overflowing the liquid level of the mixed solution into the distillation kettle by adopting an overflow method, repeating the steps for 20 times until the pore-forming agent of the polymeric white balls is extracted completely, drying the extracted polymeric white balls until the water content is 10%, and screening out the polymeric white balls with the particle size of 0.3-1.2 mm as sulfonated base balls.
TABLE 2
Example 3:
selecting macroporous polystyrene white balls with the water content of 5% and the particle size of 0.3-1.2 mm as a sulfonation matrix, mixing the white balls with sulfuric acid with the concentration of 98%, stirring the white balls with the mass ratio of 1:10 with a sulfonating agent for 1h, fully mixing the white balls with the sulfonating agent, reacting the white balls with the sulfonating agent at the temperature of 110 ℃ for 12h, cooling the white balls after the reaction is finished, placing the white balls in a water washing column, washing the white balls with deionized water to be neutral, separating sulfonated resin with the water content of 50%, and carrying out sulfhydrylation modification:
adding sulfonated resin into a reaction kettle, adding deionized water, adjusting pH=7, adding a dimercaptoethyl sulfide modifier, carrying out modification reaction for 3 hours, and washing and discharging after the modification reaction is finished to obtain the bisphenol A resin catalyst, wherein the ratio of the sulfonated resin to the deionized water to the dimercaptoethyl sulfide is 100:200:10 in parts by weight.
The obtained resin catalyst is usedThe catalyst is synthesized in bisphenol A catalysis. Loading 50ml of newly obtained catalyst into a fixed bed reactor, firstly replacing water in the catalyst with a phenol concentrated solution with the concentration not lower than 80%, and then carrying out catalytic synthesis reaction of acetone and phenol, wherein the reaction molar ratio of the phenol to the acetone is 10:1, the reaction temperature is 90 ℃, and the feeding airspeed is 1.0h -1 The reaction was carried out under a pressure of 0.4MPa, and the acetone conversion was 99.8% and the selectivity was 99.2%.
Practical researches prove that the conventional macroporous polystyrene white ball serving as a sulfonated matrix has little influence on the catalyst prepared by bisphenol A catalysis after modification, but the preparation of the macroporous polystyrene white ball is concretely as follows:
1) Polymerization
Weighing styrene, p-ethylstyrene, m-ethylstyrene, p-divinylbenzene, m-divinylbenzene, pore-forming agent and initiator according to the weight parts of table 3, loading into a mixing tank, stirring for 1.0h, and uniformly mixing the feed liquid, wherein the pore-forming agent and the initiator are conventional components, such as white oil is used as the pore-forming agent, and benzoyl peroxide is used as the initiator;
adding a water phase into a polymerization kettle, stirring and heating to 45 ℃ to enable the water phase to be completely dissolved, adding a material liquid of a mixing tank into the polymerization kettle, stirring at 110 r/min, slowly heating to 80 ℃ for polymerization reaction for 10 hours, cooling, discharging, and washing the polymerized white balls with hot water and cold water alternately for three times to obtain the polymerized white balls; the water phase is prepared from conventional dispersing agents such as alum;
2) Extracting
Adding the polymeric white balls into an extraction kettle, adding excessive solvent dichloroethane into a distillation kettle, heating to evaporate and condense the solvent in the kettle to the extraction kettle, dissolving the pore-forming agent by the solvent to form a mixed solution, overflowing the liquid level of the mixed solution into the distillation kettle by adopting an overflow method, repeating the steps for 10 times until the pore-forming agent of the polymeric white balls is extracted completely, drying the extracted polymeric white balls until the water content is 5%, and screening out the polymeric white balls with the particle size of 0.3-1.2 mm as sulfonated base balls.
TABLE 3 Table 3
Example 4:
the preparation method comprises the steps of selecting macroporous polystyrene white balls with the water content of 8% and the particle size of 0.3-1.2 mm as a sulfonation matrix, mixing the macroporous polystyrene white balls with the sulfuric acid with the concentration of 98%, stirring the mixture for 1h, fully mixing the mixture with a sulfonating agent, reacting the mixture at the temperature of 100 ℃ for 12h, cooling the mixture after the reaction is finished, placing the mixture in a water washing column, washing the mixture to be neutral by deionized water, separating sulfonated resin with the water content of 50%, and carrying out sulfhydrylation modification:
adding sulfonated resin into a reaction kettle, adding deionized water, adjusting pH=6, then adding a dimercaptoethyl sulfide modifier for modification reaction for 2 hours, and washing and discharging after finishing to obtain the bisphenol A resin catalyst, wherein the ratio of the sulfonated resin to the deionized water to the dimercaptoethyl sulfide is 100:200:4 in parts by weight.
The obtained resin catalyst is used for bisphenol A catalytic synthesis. Loading 50ml of newly obtained catalyst into a fixed bed reactor, firstly replacing water in the catalyst with a phenol concentrated solution with the concentration not lower than 80%, and then carrying out catalytic synthesis reaction of acetone and phenol, wherein the reaction molar ratio of the phenol to the acetone is 10:1, the reaction temperature is 85 ℃, and the feeding airspeed is 0.7h -1 The reaction was carried out under a pressure of 0.4MPa, and the acetone conversion was 99.1% and the selectivity was 99.3%.
Practical researches prove that the conventional macroporous polystyrene white ball serving as a sulfonated matrix has little influence on the catalyst prepared by bisphenol A catalysis after modification, but the preparation of the macroporous polystyrene white ball is concretely as follows:
1) Polymerization
Weighing styrene, p-ethylstyrene, m-ethylstyrene, p-divinylbenzene, m-divinylbenzene, pore-forming agent and initiator according to the weight parts of table 4, loading into a mixing tank, stirring for 0.5h, and uniformly mixing the feed liquid, wherein the pore-forming agent and the initiator are conventional components, such as white oil is used as the pore-forming agent, and benzoyl peroxide is used as the initiator;
adding a water phase into a polymerization kettle, stirring and heating to 50 ℃ to enable the water phase to be completely dissolved, adding a material liquid of a mixing tank into the polymerization kettle, stirring at a rotation speed of 120 r/min, slowly heating to 80 ℃ for polymerization reaction for 8 hours, cooling, discharging, and washing the polymerized white balls with hot water and cold water alternately for three times to obtain the polymerized white balls; the water phase is prepared from conventional dispersing agents such as alum;
2) Extracting
Adding the polymeric white balls into an extraction kettle, adding excessive solvent dichloroethane into a distillation kettle, heating to evaporate and condense the solvent in the kettle to the extraction kettle, dissolving the pore-forming agent by the solvent to form a mixed solution, overflowing the liquid level of the mixed solution into the distillation kettle by adopting an overflow method, repeating the steps for 14 times until the pore-forming agent of the polymeric white balls is extracted completely, drying the extracted polymeric white balls until the water content is 8%, and screening out the polymeric white balls with the particle size of 0.3-1.2 mm as sulfonated base balls.
TABLE 4 Table 4

Claims (6)

1. The resin catalyst for bisphenol A synthesis is characterized in that the catalyst is prepared by adding large-aperture sulfonated polystyrene spheres with the water content of 45-55% into deionized water, adjusting the pH value to 5-7, adding dimercaptoethyl sulfide, carrying out modification reaction for 1-3 hours, and washing with water; the weight ratio of the large-aperture sulfonated polystyrene spheres to deionized water to dimercaptoethyl sulfide is 100:200: (2-10).
2. The resin catalyst for bisphenol A synthesis according to claim 1, wherein the large-pore sulfonated polystyrene spheres are obtained by mixing polystyrene white spheres with 98% sulfuric acid sulfonating agent in a mass ratio of 1:8-12, stirring for 0.5-2 h to fully mix, at 100-120 ℃ for sulfonation for 8-20 h, cooling after the end, washing with deionized water to neutrality, and separating.
3. The resin catalyst for bisphenol A synthesis according to claim 1, wherein the water content of the polystyrene white spheres before sulfonation of the large-pore sulfonated polystyrene spheres is 5 to 10% by mass after drying and volatilizing the solvent.
4. The resin catalyst for bisphenol A synthesis according to claim 1, wherein the polystyrene white spheres before sulfonation of the large-pore sulfonated polystyrene spheres are selected as the sulfonated base spheres having a particle diameter of 0.3 to 1.2 mm.
5. The resin catalyst for bisphenol A synthesis according to claim 1, wherein the large-pore sulfonated polystyrene spheres have a pore diameter of not less than 10nm.
6. Use of the resin catalyst for bisphenol a synthesis according to any of claims 1-5 for the catalytic preparation of bisphenol a, characterized in that the process of application is: the resin catalyst for bisphenol A synthesis is filled into a catalytic reaction device, firstly, the water in the catalyst is replaced by a phenol concentrated solution with the concentration of not less than 80%, then, the catalytic synthesis reaction of acetone and phenol is carried out, the reaction mole ratio of phenol and acetone is 10:1, the reaction temperature is 80-90 ℃, and the feeding airspeed is 0.2h -1 -1h -1 Reacting at 0.2-0.4 MPa.
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